CN117092262A - Analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish - Google Patents
Analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish Download PDFInfo
- Publication number
- CN117092262A CN117092262A CN202310960585.0A CN202310960585A CN117092262A CN 117092262 A CN117092262 A CN 117092262A CN 202310960585 A CN202310960585 A CN 202310960585A CN 117092262 A CN117092262 A CN 117092262A
- Authority
- CN
- China
- Prior art keywords
- carbazole
- shellfish
- halogenated derivatives
- extraction
- dichlorocarbazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 235000015170 shellfish Nutrition 0.000 title claims abstract description 72
- 238000004458 analytical method Methods 0.000 title claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000000605 extraction Methods 0.000 claims abstract description 63
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 18
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 claims abstract description 15
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 claims abstract description 8
- CABSFELLEWZIAK-UHFFFAOYSA-N 3-chloro-9h-carbazole Chemical compound C1=CC=C2C3=CC(Cl)=CC=C3NC2=C1 CABSFELLEWZIAK-UHFFFAOYSA-N 0.000 claims abstract description 8
- FNHISDQCWYSMTO-UHFFFAOYSA-N 1,3,6,8-tetrabromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC(Br)=C3NC2=C1Br FNHISDQCWYSMTO-UHFFFAOYSA-N 0.000 claims abstract description 7
- XEUQVTHGXKXLBB-UHFFFAOYSA-N 1,3,6,8-tetrachloro-9h-carbazole Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC(Cl)=C3NC2=C1Cl XEUQVTHGXKXLBB-UHFFFAOYSA-N 0.000 claims abstract description 7
- LMYCYTOEMHSFKR-UHFFFAOYSA-N 1,3,6-tribromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1Br LMYCYTOEMHSFKR-UHFFFAOYSA-N 0.000 claims abstract description 7
- QIZKWIUIKHLXJQ-UHFFFAOYSA-N 1,8-dibromo-3,6-dichloro-9H-carbazole Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC(Br)=C3NC2=C1Br QIZKWIUIKHLXJQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- AAXKJEWUYLSARD-UHFFFAOYSA-N 1-bromo-3,6-dichloro-9H-carbazole Chemical compound BrC1=CC(=CC=2C3=CC(=CC=C3NC1=2)Cl)Cl AAXKJEWUYLSARD-UHFFFAOYSA-N 0.000 claims abstract description 7
- OJKBRICGLQOUKS-UHFFFAOYSA-N 2,3,6,7-tetrachloro-9H-carbazole Chemical compound ClC1=CC=2NC3=CC(=C(C=C3C=2C=C1Cl)Cl)Cl OJKBRICGLQOUKS-UHFFFAOYSA-N 0.000 claims abstract description 7
- BIMDTNQPZWJKPL-UHFFFAOYSA-N 3,6-dichloro-9h-carbazole Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC=C3NC2=C1 BIMDTNQPZWJKPL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000002203 pretreatment Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000010828 elution Methods 0.000 claims description 6
- 238000004811 liquid chromatography Methods 0.000 claims description 6
- 238000004885 tandem mass spectrometry Methods 0.000 claims description 6
- 238000001195 ultra high performance liquid chromatography Methods 0.000 claims description 6
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 5
- OYIGWMXXIFYAGD-UHFFFAOYSA-N 3-iodo-9h-carbazole Chemical compound C1=CC=C2C3=CC(I)=CC=C3NC2=C1 OYIGWMXXIFYAGD-UHFFFAOYSA-N 0.000 claims description 4
- CBJHFGQCHKNNJY-UHFFFAOYSA-N 4-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C=CC=C2Br CBJHFGQCHKNNJY-UHFFFAOYSA-N 0.000 claims description 4
- BKBSXIWYKWFQBX-UHFFFAOYSA-N 4-chloro-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C=CC=C2Cl BKBSXIWYKWFQBX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001514 detection method Methods 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000005909 Kieselgur Substances 0.000 description 16
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 12
- 238000010586 diagram Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 description 7
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- -1 Halogenated carbazole (polyhalogenated carbazoles Chemical class 0.000 description 3
- 150000001716 carbazoles Chemical class 0.000 description 3
- 238000000132 electrospray ionisation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002552 multiple reaction monitoring Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000583 progesterone congener Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/36—Control of physical parameters of the fluid carrier in high pressure liquid systems
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
- G01N30/724—Nebulising, aerosol formation or ionisation
- G01N30/7266—Nebulising, aerosol formation or ionisation by electric field, e.g. electrospray
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention discloses an analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish, belonging to the technical field of compound detection; the analysis method comprises the following steps: mixing shellfish samples, diatomite and florisil, placing the mixture into an extraction tank for extraction to obtain an extraction liquid, drying the extracted liquid nitrogen, and re-dissolving to obtain a sample to be detected; analyzing 11 carbazole and halogenated derivatives thereof in shellfish by using ultra-high performance liquid chromatography-tandem mass spectrometry; wherein the 11 kinds of carbazole and halogenated derivatives thereof comprise carbazole, 3-chlorocarbazole, 3-bromocarbazole, 3, 6-dichlorocarbazole, 3, 6-dibromocarbazole, 1,3, 6-tribromocarbazole, 1-bromo-3, 6-dichlorocarbazole, 1, 8-dibromo-3, 6-dichlorocarbazole, 1,3,6, 8-tetrachlorocarbazole, 1,3,6, 8-tetrabromocarbazole or 2,3,6, 7-tetrachlorocarbazole. The analysis method has good stability and the detection result has good accuracy and precision.
Description
Technical Field
The invention belongs to the technical field of compound detection, and particularly relates to an analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish.
Background
Carbazole (CZ) is a polycyclic nitrogen-containing heterocyclic organic substance, and is widely used in the fields of dyes, photoelectric materials, pesticides, and the like. Halogenated carbazole (polyhalogenated carbazoles, PHCZs) refers to a novel organic pollutant formed by substituting a hydrogen atom on a carbazole ring with a halogen atom (Cl, br or I), and the chemical structure of the novel organic pollutant is similar to that of polychlorinated dibenzofurans. More than 20 PHCZs have been detected in the environment. PHCZs has stable property, is difficult to degrade, can remain in the environment for a long time, and has the characteristics of potential durability, bioaccumulation, long-distance migration and the like. Marine shellfish belongs to mollusks, has wide distribution in southeast coast in China, has high content of fat and protein in the body, has certain nutrition and eating value, is an important aquatic resource because the special flavor is liked by people. Marine shellfish mainly live in offshore areas, usually with their bodies buried in sand mud or adsorbed on rock, have poor mobility, belong to non-selective filter feeding organisms and mainly feed on suspended matter and silt spoilage in water bodies. Research shows that shellfish has strong tolerance and high accumulation of heavy metals, so carbazole and halogenated derivatives thereof in seawater or sediment can easily enter the body through enrichment of shellfish. Carbazole and halogenated derivatives thereof are used as a novel pollutant, environmental pollution detection, toxicological tests and the like are still in a starting stage, and detection technical standards of a system are not established yet, so that the research of relevant environmental monitoring and pollutant migration enrichment is affected. Therefore, it is necessary to establish an analysis method of various halogenated carbazoles in shellfish, which provides a scientific basis for monitoring the pollution status of halogenated carbazoles in shellfish.
Disclosure of Invention
The invention aims to provide a sample pretreatment method for detecting carbazole and halogenated derivatives thereof in shellfish, which has good extraction effect and high recovery rate of target compounds.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a sample pretreatment method for detecting carbazole and halogenated derivatives thereof in shellfish comprises the steps of uniformly mixing shellfish samples, diatomite and florisil, wherein the mass ratio of the shellfish samples to the diatomite to the florisil is 1:0.5-5:0.5-5, placing the shellfish samples, the diatomite and the florisil into an extraction tank for extraction to obtain an extraction liquid, drying extracted liquid nitrogen, and re-dissolving to obtain a sample to be detected. The shellfish sample matrix is complex, and the contained CZ and PHCZs concentrations are low, so that the selection of a proper sample pretreatment method is the key of a detection method. According to the sample pretreatment method, diatomite and florisil in a specific proportion are used as extraction media, so that the target compound carbazole and halogenated derivatives thereof have high recovery rate, and the accuracy and the qualitation of the analysis method are improved.
In one embodiment, the mass ratio of shellfish sample, diatomaceous earth, and florisil is 1:1-2:1-2.
In one embodiment, the diatomaceous earth is a sulfhydrylated diatomaceous earth or a sulfonated diatomaceous earth. The sulfhydrylation diatomite or the sulfonated diatomite is used as an extraction medium, so that the extraction effect can be improved, and the extraction efficiency is improved.
In a preferred embodiment, the mass ratio of shellfish sample, sulfhydryl diatomaceous earth, and florisil is 1:1-2:1-2.
In a preferred embodiment, the mass ratio of shellfish sample, sulfonated diatomaceous earth, and florisil is 1:1-2:1-2.
In a preferred embodiment, the process for preparing the mercaptodiatomaceous earth comprises:
acid treatment is carried out on diatomite to obtain acidified diatomite; and, a step of, in the first embodiment,
the acidified diatomite and mercaptopropyl trimethoxy silane are reacted to obtain the mercaptoated diatomite.
In a more preferred embodiment, the mass ratio of the acidified diatomaceous earth to mercaptopropyl trimethoxysilane is from 1:0.5 to 0.8.
Further preferably, the preparation method of the sulfhydrylation diatomite comprises the following steps:
adding diatomite into 1-3M hydrochloric acid solution for acid treatment for 0.5-5h, then washing with distilled water to be neutral, and drying to obtain acidified diatomite; and, a step of, in the first embodiment,
adding acidified diatomite and mercaptopropyl trimethoxy silane into methanol, uniformly stirring, reacting for 6-12h at 60-80 ℃, filtering, washing with absolute ethyl alcohol and deionized water in sequence, and drying to obtain the mercaptoated diatomite, wherein the mass ratio of the acidified diatomite to the mercaptopropyl trimethoxy silane to the methanol is 1:0.5-0.8:80-120.
In a preferred embodiment, the sulfonated diatomaceous earth is prepared by:
acid treatment is carried out on diatomite to obtain acidified diatomite;
reacting acidified diatomite with mercaptopropyl trimethoxy silane to obtain mercaptoated diatomite; and, a step of, in the first embodiment,
the sulfhydrylation diatomite is oxidized by hydrogen peroxide solution to obtain sulfonated diatomite.
In a more preferred embodiment, the mass ratio of the acidified diatomaceous earth to mercaptopropyl trimethoxysilane is from 1:0.5 to 0.8.
In a more preferred embodiment, the concentration of the hydrogen peroxide solution is in the range of 20 to 50wt%.
In a more preferred embodiment, the ratio of the amount of mercaptodiatomaceous earth to hydrogen peroxide solution is 1:20 to 50mL.
In a preferred embodiment, the sulfonated diatomaceous earth is prepared by:
adding diatomite into 1-3M hydrochloric acid solution for acid treatment for 0.5-5h, then washing with distilled water to be neutral, and drying to obtain acidified diatomite; and, a step of, in the first embodiment,
adding acidified diatomite and mercaptopropyl trimethoxy silane into methanol, uniformly stirring, reacting for 6-12h at 60-80 ℃, filtering, washing with absolute ethyl alcohol and deionized water in sequence, and drying to obtain mercaptodiatomite, wherein the mass ratio of the acidified diatomite to the mercaptopropyl trimethoxy silane to the methanol is 1:0.5-0.8:80-120;
adding 20-50wt% hydrogen peroxide solution into the sulfhydrylation diatomite, stirring and reacting for 12-24h at 40-70 ℃ with the dosage ratio of the sulfhydrylation diatomite to the hydrogen peroxide solution being 1:20-50mL, filtering, washing with absolute ethyl alcohol and deionized water in sequence, and drying to obtain the sulfonated diatomite.
In one embodiment, the extraction solvent for extraction is methylene chloride.
The concentration of 11 carbazole and halogenated derivatives thereof in shellfish is low, so that the selection of a proper extraction method is the key of an analysis method. In order to improve the extraction effect of 11 carbazole and halogenated derivatives thereof in shellfish and further improve the accuracy and the quality of the analysis method, in a preferred embodiment, the extraction solvent for extraction is dichloromethane and bromochloromethane, and the volume ratio of the dichloromethane to the bromochloromethane is 100:5-15.
In one embodiment, the extraction conditions are 80-120deg.C, 1000-2000psi, the extraction time is 2-10min, and the cycle is 1-5 times.
In a preferred embodiment, the extraction conditions are 100-110℃and 1000-2000psi, the extraction time is 3-8min, and the cycle is 2-3 times.
In one embodiment, shellfish samples, diatomite and florisil are evenly mixed, the mass ratio of the shellfish samples, the diatomite and the florisil is 1:1-2:1-2, the shellfish samples, the diatomite and the florisil are placed into an extraction tank filled with a glass fiber filter membrane, extraction is carried out for 2-10min at 80-120 ℃ under the condition of 1000-2000psi by using an extraction solvent, extraction liquid is obtained by circulating extraction for 1-5 times, extracted liquid nitrogen is dried, acetonitrile-water with the volume ratio of 1:0.5-1.5 is used for redissolution, and the use amount ratio of the shellfish samples and the acetonitrile-water is 1g:100-500 mu L, so that samples to be detected are obtained.
In one embodiment, shellfish samples, sulfhydrylated diatomite and florisil are evenly mixed, the mass ratio of the shellfish samples, the sulfhydrylated diatomite and the florisil is 1:1-2:1-2, the shellfish samples, the sulfhydrylated diatomite and the florisil are placed into an extraction tank filled with a glass fiber filter membrane, the extraction solvent is utilized to extract for 2-10min under the conditions of 80-120 ℃ and 1000-2000psi, the extraction liquid is obtained by circulating the extraction for 1-5 times, the extracted liquid nitrogen is dried, acetonitrile-water with the volume ratio of 1:0.5-1.5 is used for re-dissolving, and the dosage ratio of the shellfish samples and the acetonitrile-water is 1g:100-500 mu L, thus obtaining the sample to be detected.
In one embodiment, shellfish samples, sulfonated diatomite and florisil are evenly mixed, the mass ratio of the shellfish samples to the sulfonated diatomite to the florisil is 1:1-2:1-2, the shellfish samples, the sulfonated diatomite and the florisil are placed into an extraction tank filled with a glass fiber filter membrane, extraction is carried out for 2-10min at the temperature of 80-120 ℃ under the pressure of 1000-2000psi by using an extraction solvent, extraction liquid is obtained by circulating extraction for 1-5 times, extracted liquid nitrogen is dried by blowing, acetonitrile-water with the volume ratio of 1:0.5-1.5 is used for re-dissolution, and the dosage ratio of the shellfish samples to the acetonitrile-water is 1g:100-500 mu L, thus obtaining the sample to be detected.
The invention also discloses application of the sample pretreatment method in detecting carbazole and halogenated derivatives thereof in shellfish.
The invention aims to provide an analysis method for detecting 11 kinds of carbazole and halogenated derivatives thereof in shellfish, which has high recovery rate of target compounds and good stability, accuracy and precision.
The technical scheme adopted by the invention for achieving the purpose is as follows:
an analysis method for detecting 11 kinds of carbazole and halogenated derivatives thereof in shellfish utilizes ultra-high performance liquid chromatography tandem mass spectrometry to analyze 11 kinds of carbazole and halogenated derivatives thereof in shellfish; the sample to be tested is obtained according to the sample pretreatment method;
among them, 11 kinds of carbazole and halogenated derivatives thereof include Carbazole (CZ), 3-chlorocarbazole (3-CCZ), 3-bromocarbazole (3-BCZ), 3, 6-dichlorocarbazole (3, 6-CCZ), 3, 6-dibromocarbazole (3, 6-BCZ), 1,3, 6-tribromocarbazole (1, 3, 6-BCZ), 1-bromo-3, 6-dichlorocarbazole (1-B-3, 6-CCZ), 1, 8-dibromo-3, 6-dichlorocarbazole (1, 8-B-3, 6-CCZ), 1,3,6, 8-tetrachlorocarbazole (1, 3,6, 8-CCZ), 1,3,6, 8-tetrabromocarbazole (1, 3,6, 8-BCZ) or 2,3,6, 7-tetrachlorocarbazole (2, 3,6, 7-CCZ).
Firstly, the shellfish sample is pretreated by adopting the sample pretreatment method, so that the target compound carbazole and halogenated derivatives thereof have higher recovery rate; and then, adopting ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) to analyze carbazole and/or carbazole halogenated derivatives in shellfish, wherein the analysis method has good stability and the detection result has good accuracy and precision.
In one embodiment, the mobile phase of the liquid chromatograph is: a is acetonitrile and B is 5mmol/L ammonium formate solution.
In one embodiment, the mobile phase of the liquid chromatograph is: a is acetonitrile and B is 5mmol/L ammonium formate solution. The mobile phase compared to liquid chromatography is: a is acetonitrile, B is 5mmol/L ammonium formate solution, and the separation effect of the mobile phase is better and the sensitivity is higher.
In one embodiment, during liquid chromatography, the following elution procedure is performed, based on 100% total mobile phase volume: at 0-8min, the volume ratio of the mobile phase A to the mobile phase B is 50-90:50-10.
In a preferred embodiment, during liquid chromatography, the following elution procedure is performed, based on 100% total volume of mobile phase:
0-1min, wherein the volume ratio of the mobile phase A to the mobile phase B is 50:50;
1-3min, wherein the volume ratio of the mobile phase A to the mobile phase B is 90:10;
3-6.9min, the volume ratio of the mobile phase A to the mobile phase B is 90:10;
6.9-7min, wherein the volume ratio of the mobile phase A to the mobile phase B is 50:50;
7-8min, the volume ratio of the mobile phase A to the mobile phase B is 50:50.
In one embodiment, the flow rate is from 0.1 to 0.5mL/min.
In a preferred embodiment, the flow rate is 0.3mL/min.
In one embodiment, the sample is introduced in an amount of 5 to 10. Mu.L.
In a preferred embodiment, the sample is introduced in an amount of 10. Mu.L.
In one embodiment, the chromatographic conditions are: chromatographic column: ACQUITY UPLC CSH C18, 2.1X100mm,1.7 μm; column temperature: 35 ℃; flow rate: 0.3mL/min; sample injection amount: 10 mu L. During the liquid chromatography, the following elution procedure was performed, based on 100% total volume of mobile phase:
0-1min, wherein the volume ratio of the mobile phase A to the mobile phase B is 50:50;
1-3min, wherein the volume ratio of the mobile phase A to the mobile phase B is 90:10;
3-6.9min, the volume ratio of the mobile phase A to the mobile phase B is 90:10;
6.9-7min, wherein the volume ratio of the mobile phase A to the mobile phase B is 50:50;
7-8min, the volume ratio of the mobile phase A to the mobile phase B is 50:50.
In one embodiment, the mass spectrometry conditions are: the ion source is electrospray ionization; the scanning mode is negative ion scanning; the collection mode is multi-reaction monitoring.
In one embodiment, the above 11 carbazole and halogenated derivatives thereof standard substances are taken, dissolved by acetonitrile and respectively prepared into 10mg/mL single standard stock solution; respectively taking 1.0mL of 11 single standard stock solutions, dissolving the stock solutions with acetonitrile and preparing a mixed standard intermediate solution with the concentration of 1 mg/mL; and (3) adopting UPLC-MS/MS to carry out measurement and analysis, and drawing a standard working curve by taking the peak area ratio as an ordinate and the ratio of the mass concentration to the internal standard concentration as an abscissa.
In one embodiment, a sample to be detected is measured by adopting UPLC-MS/MS to obtain a sample chromatogram, and the sample chromatogram is compared with a standard curve to carry out qualitative detection; and determining the parent ions, the ion, the collision voltage and the capillary voltage of each substance by using the tuning function of the UPLC-MS/MS instrument, and quantitatively detecting the progestogen in the working solution by using the parameters.
The invention also provides the use of the above method in the detection of carbazole and/or carbazole halogenated derivatives in shellfish, selected from at least one of carbazole, 3-chlorocarbazole, 3-bromocarbazole, 3-iodocarbazole, 4-chlorocarbazole, 4-bromocarbazole, 3, 6-dichlorocarbazole, 3, 6-dibromocarbazole, 2, 7-dibromocarbazole, 1,3, 6-tribromocarbazole, 1-bromo-3, 6-dichlorocarbazole, 1, 8-dibromo-3, 6-dichlorocarbazole, 1,3,6, 8-tetrachlorocarbazole, 1,3,6, 8-tetrabromocarbazole or 2,3,6, 7-tetrachlorocarbazole.
The invention aims to provide an analysis method for detecting 11 kinds of carbazole and halogenated derivatives thereof in shellfish.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a detection method of carbazole and/or carbazole halogenated derivatives in shellfish comprises,
detecting carbazole and/or carbazole halogenated derivatives in a shellfish sample to be detected by utilizing ultra-high performance liquid chromatography-tandem mass spectrometry; the shellfish sample to be detected is obtained according to the sample pretreatment method;
wherein the carbazole and/or carbazole halogenated derivative is selected from at least one of carbazole, 3-chlorocarbazole, 3-bromocarbazole, 3-iodocarbazole, 4-chlorocarbazole, 4-bromocarbazole, 3, 6-dichlorocarbazole, 3, 6-dibromocarbazole, 2, 7-dibromocarbazole, 1,3, 6-tribromocarbazole, 1-bromo-3, 6-dichlorocarbazole, 1, 8-dibromo-3, 6-dichlorocarbazole, 1,3,6, 8-tetrachlorocarbazole, 1,3,6, 8-tetrabromocarbazole or 2,3,6, 7-tetrachlorocarbazole.
Firstly, uniformly mixing a shellfish sample with diatomite and florisil, extracting by an accelerated solvent extractor, and then analyzing 11 kinds of carbazole and halogenated derivatives thereof in shellfish by utilizing ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS); the average recovery rate of 11 carbazole and halogenated derivatives thereof is 79.25% -108.66%, the relative standard deviation is 3.71% -8.34%, and the method is stable and reliable, has good accuracy and precision, and can meet the requirement of simultaneously detecting 11 carbazole and halogenated derivatives thereof in shellfish.
The invention has the following beneficial effects: firstly, the shellfish sample is pretreated by adopting the sample pretreatment method, so that the target compound carbazole and halogenated derivatives thereof have higher recovery rate; and then, adopting ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) to analyze carbazole and/or halogenated derivatives of carbazole in shellfish, wherein the average recovery rate of 11 carbazole and halogenated derivatives thereof is 79.25% -108.66%, and the relative standard deviation is 3.71% -8.34%.
Drawings
FIG. 1 is a CZ ion fragment diagram;
FIG. 2 is a 3-CCZ ion fragment diagram;
FIG. 3 is a 3-BCZ ion fragment diagram;
FIG. 4 is a fragment diagram of 1-B-3,6-CCZ ions;
FIG. 5 is a fragment diagram of 1,8-B-3,6-CCZ ions;
FIG. 6 is a diagram of 1,3,6,8-BCZ ion fragment;
FIG. 7 is a 3,6-CCZ ion fragment diagram;
FIG. 8 is a diagram of 2,3,6,7-CCZ ion fragments;
FIG. 9 is a diagram of 1,3,6,8-CCZ ion fragments;
FIG. 10 is a 3,6-BCZ ion fragment diagram;
FIG. 11 is a diagram of 1,3,6-BCZ ion fragment;
FIG. 12 is a total ion flow diagram of 11 carbazole and their halogenated derivatives;
FIG. 13 is an infrared spectrum of diatomaceous earth, example 6 obtained thiolated diatomaceous earth, and example 7 obtained sulfonated diatomaceous earth;
FIG. 14 shows the effect of pretreatment extractant on extraction efficiency;
FIG. 15 shows the effect of diatomaceous earth for pretreatment on the extraction effect.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The experimental methods in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1: analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish
1. Instrument and reagent
Waters Xevo TQ-XS ultra-high performance liquid chromatography-triple quadrupole tandem mass spectrometer (Waters, inc. USA); dionex ASE 350 accelerated solvent extractor (sammer, feier technologies, usa); AVANTIJ-E high capacity high speed refrigerated centrifuge (BEAKMAN Co., USA); n-2110 nitrogen-blown concentrator (EYELA Co., japan); BSA224S-CW electronic balance (precision 0.1mg, sidoriscom instruments Co., germany); multiReax porous bit vortex oscillator (Haideff Corp., germany); milli-Q ultra-pure water machine (Miibo, USA).
Acetone, dichloromethane, ethyl acetate, acetonitrile were all of chromatographic grade and were purchased from Merck, germany.
2. Analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish
2.1 preparation of Standard solution
Accurately weighing or absorbing the 11 carbazole and halogenated derivative standard substances thereof, dissolving the carbazole and halogenated derivative standard substances with acetonitrile, and preparing single standard stock solutions of 10mg/mL respectively. 1.0mL of 11 single standard stock solutions are accurately sucked into a 10 mL volumetric flask respectively, dissolved with acetonitrile and prepared into a mixed standard intermediate solution of 1 mg/mL. Stored at-20deg.C in dark place for 2 months.
2.2 sample pretreatment
2.00 samples g were weighed, mixed with 3.00g diatomaceous earth, 3.00g florisil (accurate to 0.01 g) and placed into an extraction cell with a glass fiber filter membrane on the bottom. Dichloromethane (chromatographic purity) is used as an extraction solvent, extraction is carried out for 5 min at the temperature of 100 ℃ and the pressure of 1500 psi, the cyclic extraction is carried out for 2 times, after the extraction is finished, the extracted liquid nitrogen is blown and concentrated to near dryness, and 200 mu L of acetonitrile-water (1:1/V/V) is used for redissolution, and the solution is to be tested.
2.3 chromatographic conditions
Chromatographic column: ACQUITY UPLC CSH C18 (2.1X100 mm,1.7 μm); column temperature: flow rate at 35 ℃): 0.3mL/min; sample injection amount: 10. Mu.L; mobile phase: a is acetonitrile, B is 5mmol/L ammonium formate solution, and the specific gradient elution procedure is shown in Table 1.
Table 1 mobile phase elution procedure for liquid chromatography
| Time/min | 1 | 3 | 6.9 | 7 | 8 |
| Mobile phase a ratio/% | 50 | 90 | 90 | 50 | 50 |
| Mobile phase B ratio/% | 50 | 10 | 10 | 50 | 50 |
2.4 Mass Spectrometry conditions
The ion source is electrospray ionization (ESI); the scanning mode is negative ion scanning; the collection mode is Multiple Reaction Monitoring (MRM). Specific mass spectral parameters for the 11 carbazole and their halogenated derivatives are shown in table 2.
Table 2 mass spectral parameters of 11 carbazole and its halogenated derivatives
2.5 methodological validation
Preparing a series of mixed standard solutions with concentration changing step by step, adopting UPLC-MS/MS to perform measurement and analysis, taking the peak area ratio as an ordinate (Y), and the ratio of the mass concentration to the internal standard concentration as an abscissa (X, ng/ml), and drawing a standard working curve to obtain the linear range, linear regression equation, correlation coefficient, detection limit and quantitative limit of 11 carbazole and halogenated derivatives thereof, as shown in Table 3.
TABLE 3 Linear range, linear regression equation, correlation coefficient of 11 carbazole and halogenated derivatives thereof
Taking blank shellfish samples, adding a proper amount of 11 carbazole and halogenated derivatives thereof mixed standard working solutions, wherein the standard adding level is respectively 1 times of the quantitative limit, 3 times of the quantitative limit and 10 times of the quantitative limit of each PHCZs, preparing 6 parts of to-be-detected liquid at each concentration level in parallel, and carrying out analysis and determination, wherein the results are shown in figures 1-13 and Table 4. The average recovery rate of 11 carbazole and halogenated derivatives thereof is 79.25% -108.66%, the relative standard deviation is 3.71% -8.34%, and the method is stable and reliable, has good accuracy and precision, and can meet the requirement of simultaneously detecting 11 carbazole and halogenated derivatives thereof in shellfish.
TABLE 4 average recovery and relative standard deviation of 11 carbazole and halogenated derivatives thereof in shellfish samples
Example 2: analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish
The analytical method of this example is essentially the same as that of example 1, except that: the extraction solvent used for pretreatment of the sample in this example is a mixed solution of dichloromethane and bromochloromethane, and the volume ratio of dichloromethane to bromochloromethane is 100:5.
Example 3: analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish
The analytical method of this example is essentially the same as that of example 1, except that: the extraction solvent used for pretreatment of the sample in this example is a mixed solution of dichloromethane and bromochloromethane, and the volume ratio of dichloromethane to bromochloromethane is 100:10.
Example 4: analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish
The analytical method of this example is essentially the same as that of example 1, except that: the extraction solvents used for pretreatment of the sample in this example were methylene chloride and methanol, and the volume ratio of methylene chloride to methanol was 100:15.
Example 5: analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish
The analytical method of this example is essentially the same as that of example 1, except that: the extraction solvent used for pretreatment of the sample in this example was methylene chloride and n-hexane, and the volume ratio of methylene chloride to n-hexane was 100:20.
Example 6:
analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish
The analytical method of this example is essentially the same as that of example 1, except that: the diatomaceous earth used for pretreatment of the sample in this example was mercaptodiatomaceous earth. The preparation method of the sulfhydrylation diatomite comprises the following steps:
adding diatomite into a 2M hydrochloric acid solution for acid treatment for 1h, washing with distilled water to be neutral, and drying to obtain acidified diatomite; and, a step of, in the first embodiment,
adding acidified diatomite and mercaptopropyl trimethoxy silane into methanol, stirring uniformly, reacting for 8 hours at 70 ℃, filtering, washing with absolute ethyl alcohol and deionized water in sequence, and drying to obtain the mercaptoated diatomite, wherein the mass ratio of the acidified diatomite to the mercaptopropyl trimethoxy silane to the methanol is 1:0.8:100.
Example 7:
analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish
The analytical method of this example is essentially the same as that of example 1, except that: the diatomaceous earth used for pretreatment of the sample in this example was mercaptodiatomaceous earth. The preparation method of the sulfonated diatomite comprises the following steps:
adding diatomite into a 2M hydrochloric acid solution for acid treatment for 1h, washing with distilled water to be neutral, and drying to obtain acidified diatomite; and, a step of, in the first embodiment,
adding acidified diatomite and mercaptopropyl trimethoxy silane into methanol, uniformly stirring, reacting at 70 ℃ for 8 hours, filtering, washing with absolute ethyl alcohol and deionized water in sequence, and drying to obtain mercaptoated diatomite, wherein the mass ratio of the acidified diatomite to the mercaptopropyl trimethoxy silane to the methanol is 1:0.8:100;
adding 30wt% hydrogen peroxide solution into the sulfhydrylation diatomite, stirring and reacting for 12 hours at 55 ℃ with the dosage ratio of the sulfhydrylation diatomite to the hydrogen peroxide solution being 1:40mL, filtering, washing with absolute ethyl alcohol and deionized water in sequence, and drying to obtain the sulfonated diatomite.
Test example 1:
diatomaceous earth, the thiolated diatomaceous earth obtained in example 6 and the sulfonated diatomaceous earth obtained in example 7 were tested by fourier infrared spectrometer, and the wave number range was controlled to 400-4000cm by KBr tabletting technique -1 Resolution of 4cm -1 The sample was scanned 32 times. FIGS. 13 (a), (b) and (c) are the IR spectra of diatomaceous earth, example 6 obtained thiolated diatomaceous earth, and example 7 obtained sulfonated diatomaceous earth, respectively. As can be seen from a comparison of FIGS. 13 (a), (b) and (c), FIG. 13 (b) shows a measurement of 2925cm -1 And 2870cm -1 The characteristic peak of methylene appears nearby, 2550cm -1 The characteristic peak of sulfhydryl appears nearby, 550-600cm -1 C-S characteristic peaks appear in the range, which indicates that the sulfhydryl diatomite is successfully prepared; since the characteristic peak of s=o in the sulfonic acid group and the characteristic peak of si—o overlap, the characteristic peak is not obvious, but is 3450cm in fig. 13 (b) -1 The characteristic peak of hydroxyl near the position is strengthened, and the characteristic peak of sulfhydryl group is weakened, which indicates that the sulfonated diatomite is successfully prepared.
The test example examines the influence of the extractant for pretreatment of the samples of examples 1-5 on the extraction effect, the standard concentration is 1.0 mug/kg, and the result is shown in fig. 14, and it can be seen that the extraction effect of examples 2-4 is better than that of examples 1 and 5, which indicates that the extraction effect is better when the extraction solvent for extraction is dichloromethane and bromochloromethane with the volume ratio of 100:5-15.
The test example examines the influence of diatomite for pretreatment of samples of the embodiment 1 and the embodiment 6-7 on the extraction effect, the standard concentration is 1.0 mug/kg, and the result is shown in fig. 15, and the extraction effect of the embodiment 6-7 is better than that of the embodiment 1, which shows that the extraction effect can be improved by taking the sulfhydrylation diatomite or the sulfonated diatomite as the extraction medium, the extraction efficiency is improved, and the effect of the sulfonated diatomite is better than that of the sulfhydrylation diatomite.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art, and are not described herein.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made without departing from the spirit and scope of the invention.
Claims (10)
1. A sample pretreatment method for detecting carbazole and halogenated derivatives thereof in shellfish comprises the steps of uniformly mixing shellfish samples, diatomite and florisil, wherein the mass ratio of the shellfish samples to the diatomite to the florisil is 1:0.5-5:0.5-5, placing the shellfish samples, the diatomite and the florisil into an extraction tank for extraction to obtain an extraction liquid, drying extracted liquid nitrogen, and re-dissolving to obtain a sample to be detected.
2. The sample pretreatment method according to claim 1, wherein: the extraction solvent for extraction comprises methylene dichloride.
3. The sample pretreatment method according to claim 1, wherein: the extraction conditions are 80-120 ℃, 1000-2000psi, the extraction time is 2-10min, and the cycle is 1-5 times.
4. Use of the sample pretreatment method according to claim 1 for detecting carbazole and halogenated derivatives thereof in shellfish.
5. An analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish utilizes ultra-high performance liquid chromatography tandem mass spectrometry to analyze 11 carbazole and halogenated derivatives thereof in a sample to be detected; the sample to be tested is obtained according to the sample pretreatment method of any one of claims 1 to 3;
wherein the 11 carbazole and halogenated derivatives thereof comprise carbazole, 3-chlorocarbazole, 3-bromocarbazole, 3, 6-dichlorocarbazole, 3, 6-dibromocarbazole, 1,3, 6-tribromocarbazole, 1-bromo-3, 6-dichlorocarbazole, 1, 8-dibromo-3, 6-dichlorocarbazole, 1,3,6, 8-tetrachlorocarbazole, 1,3,6, 8-tetrabromocarbazole or 2,3,6, 7-tetrachlorocarbazole.
6. The method of analysis according to claim 5, wherein: the mobile phase of the liquid chromatograph is: a is acetonitrile and B is 5mmol/L ammonium formate solution.
7. The method of analysis according to claim 5, wherein: in the liquid chromatography process, the following elution procedure was performed, based on 100% total volume of mobile phase: at 0-8min, the volume ratio of the mobile phase A to the mobile phase B is 50-90:50-10.
8. The method of analysis according to claim 5, wherein: the flow rate of the mobile phase is 0.1-0.5mL/min.
9. Use of the method according to any one of claims 5-8 for detecting carbazole and/or carbazole halogenated derivatives in shellfish, selected from at least one of carbazole, 3-chlorocarbazole, 3-bromocarbazole, 3-iodocarbazole, 4-chlorocarbazole, 4-bromocarbazole, 3, 6-dichlorocarbazole, 3, 6-dibromocarbazole, 2, 7-dibromocarbazole, 1,3, 6-tribromocarbazole, 1-bromo-3, 6-dichlorocarbazole, 1, 8-dibromo-3, 6-dichlorocarbazole, 1,3,6, 8-tetrachlorocarbazole, 1,3,6, 8-tetrabromocarbazole or 2,3,6, 7-tetrachlorocarbazole.
10. The method for detecting carbazole and/or carbazole halogenated derivatives in shellfish utilizes ultra-high performance liquid chromatography tandem mass spectrometry to detect carbazole and/or carbazole halogenated derivatives in shellfish samples to be detected; the shellfish sample to be tested is obtained according to the sample pretreatment method of any one of claims 1-3;
wherein the carbazole and/or carbazole halogenated derivative is selected from at least one of carbazole, 3-chlorocarbazole, 3-bromocarbazole, 3-iodocarbazole, 4-chlorocarbazole, 4-bromocarbazole, 3, 6-dichlorocarbazole, 3, 6-dibromocarbazole, 2, 7-dibromocarbazole, 1,3, 6-tribromocarbazole, 1-bromo-3, 6-dichlorocarbazole, 1, 8-dibromo-3, 6-dichlorocarbazole, 1,3,6, 8-tetrachlorocarbazole, 1,3,6, 8-tetrabromocarbazole or 2,3,6, 7-tetrachlorocarbazole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310960585.0A CN117092262A (en) | 2023-08-02 | 2023-08-02 | Analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310960585.0A CN117092262A (en) | 2023-08-02 | 2023-08-02 | Analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117092262A true CN117092262A (en) | 2023-11-21 |
Family
ID=88769070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310960585.0A Pending CN117092262A (en) | 2023-08-02 | 2023-08-02 | Analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117092262A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114354790A (en) * | 2021-12-28 | 2022-04-15 | 舟山市食品药品检验检测研究院 | Method for detecting 7 halogenated carbazole compounds in aquatic product |
| CN114814054A (en) * | 2022-04-14 | 2022-07-29 | 舟山市食品药品检验检测研究院 | Method for detecting 10 halogenated carbazole compounds in marine sediments |
| CN115963205A (en) * | 2022-12-29 | 2023-04-14 | 广电计量检测（沈阳）有限公司 | Method for determining content of diazepam, chlorpromazine and ribavirin in animal derived food by accelerating solvent extraction-liquid chromatography-mass spectrometry |
-
2023
- 2023-08-02 CN CN202310960585.0A patent/CN117092262A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114354790A (en) * | 2021-12-28 | 2022-04-15 | 舟山市食品药品检验检测研究院 | Method for detecting 7 halogenated carbazole compounds in aquatic product |
| CN114814054A (en) * | 2022-04-14 | 2022-07-29 | 舟山市食品药品检验检测研究院 | Method for detecting 10 halogenated carbazole compounds in marine sediments |
| CN115963205A (en) * | 2022-12-29 | 2023-04-14 | 广电计量检测（沈阳）有限公司 | Method for determining content of diazepam, chlorpromazine and ribavirin in animal derived food by accelerating solvent extraction-liquid chromatography-mass spectrometry |
Non-Patent Citations (5)
| Title |
|---|
| ELENA LBANEZ 等: "绿色萃取技术原理、进展与应用", 1 December 2021, 中国轻工业出版社, pages: 66 - 72 * |
| HONGYAN XU 等: "High throughput extraction strategy for simultaneous analysis of 19 tetrabromobisphenol A and halogenated carbazole analogs in seafood", FOOD CHEMISTRY, vol. 350, 8 February 2021 (2021-02-08), pages 1 - 10, XP086519345, DOI: 10.1016/j.foodchem.2021.129214 * |
| WENXIU ZHOU 等: "Analysis of polyhalogenated carbazoles in sediment using liquid chromatography–tandem mass spectrometry", ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY, vol. 170, 5 December 2018 (2018-12-05), pages 148 - 155 * |
| 彭露: "中国近海海域沉积物中卤代咔唑的时空分布", 中国优秀硕士学位论文全文数据库, no. 10, 15 October 2022 (2022-10-15), pages 010 - 46 * |
| 田丙正 等: "加速溶剂萃取和净化-气相色谱/三重四极杆串联质谱法测定水体沉积物中多氯联苯", 分析试验室, vol. 36, no. 7, 31 July 2017 (2017-07-31), pages 785 - 789 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110243980B (en) | High-throughput detection method for 92 forbidden industrial dyes in food | |
| CN109696499B (en) | High-sensitivity determination method for nitrosamine in water based on high-resolution mass spectrum | |
| CN112684069A (en) | Method for measuring methylnaphthalene compound in water | |
| CN113391015A (en) | Method for detecting 14 phenolic compounds in soil | |
| CN109828051B (en) | Method for detecting toxic compound | |
| CN109828071B (en) | Method for simultaneously detecting 9 water-infused drug residues in pork | |
| CN108414643B (en) | Liquid chromatography-triple quadrupole mass spectrometry detection method for biogenic amine in chilled chicken | |
| CN108760920B (en) | Method for determining residual quantity of cyazofamid and metabolites thereof based on HPLC-MSMS method | |
| CN113376305A (en) | Solid-phase membrane extraction gas chromatography-mass spectrometry detection method for carbazole and polyhalogen carbazole in water body | |
| CN108956812B (en) | Method for detecting water-soluble organic chloride pesticide residue in soil | |
| CN117092262A (en) | Analysis method for detecting 11 carbazole and halogenated derivatives thereof in shellfish | |
| CN113970609B (en) | Sediment organic phosphate and metabolite LC-MS/MS analysis method | |
| CN114166974B (en) | Method for detecting triethylamine in soil and sediment by gas chromatography-mass spectrometry | |
| CN111366643B (en) | Detection method of OLED material intermediate | |
| CN109444293A (en) | The detection method of endogenous water-soluble B vitamin in a kind of fresh tobacco leaves | |
| CN111220722B (en) | Method for simultaneously determining 8 p-hydroxybenzoate compounds in soil | |
| CN114814054A (en) | Method for detecting 10 halogenated carbazole compounds in marine sediments | |
| CN111337610B (en) | Method for detecting trace estrogen, nonyl phenol and bisphenol A in complex environment matrix | |
| CN113533570A (en) | Analysis method for main metabolites of organophosphorus flame retardant in sediment | |
| CN114002355A (en) | Solid phase extraction column for simultaneously enriching and purifying nine mycotoxins in agricultural products | |
| CN112630329A (en) | Method for detecting tetraethyl lead in water by negative pressure headspace gas chromatography-mass spectrometry | |
| CN111693639B (en) | Confirmation analysis method for detecting penicillin G residue in poultry tissue, poultry egg or pork | |
| CN111257442A (en) | Method for separating and enriching 16 organophosphorus pesticides in water environment | |
| CN100395548C (en) | Detecting method of 4-nonyl phenol in waste water or regenerated water | |
| CN114487189B (en) | Method for determining aflatoxin B1 in food based on dispersion extraction technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |